Perfume-containing compositions containing certain oximes as olfactory agents

ABSTRACT

The use of certain oximes as olfactory agents in perfume compositions is described. The oximes are those of seven to 10 carbon atom aliphatic aldehydes and Ketones, excluding oximes of saturated, straight-chain aldehydes. Numerous examples showing the use of the oximes in various perfume compositions are given, as well as examples showing the preparation and identifying properties of the following 3 novel oximes: 3,7-dimethyloctanal oxime; 2,6-dimethyl-5-heptenal oxime and 3-methylheptan-5-one oxime.

United States Patent Dahill, Jr.

[451 Jan.25,l972

[54] PERFUME-CONTAINING COMPOSITIONS CONTAINING CERTAIN OXIMES AS OLFACTORY AGENTS [72] Inventor: Robert T. Dahill, Jr., Perth Amboy, NJ.

[73] Assignee: Givaudan Corporation, Clifton, NJ.

[22] Filed: Feb. 14, 1967 [2]] Appl. No.: 617,761

[52] 0.5. CI ..252/522, 424/45, 424/69 [5|] Int. Cl. ..A61k 7/00, Cl lb 9/00 [58] Field of Search ..252/522; 260/566 5 6] References Cited OTHER PUBLICATIONS Simonsen, The Terpenes, Cambridge Univ. Press, Vol. I I93 I pp. 59, 60, 64, 8|, 82

Primary Examiner-Albert T. Meyers Assistant Examiner-A. P. Fagelson Attorney-Richards and Cifelli, George D. Richards and Thomas Cifelli, Jr.

[ ABSTRACT 13 Claims, No Drawings PERFUME-CONTAINING COMPOSITIONS CONTAINING CERTAIN OXIMES AS OLFACTORY AGENTS The present invention relates to perfume-containing compositions containing certain oximes as olfactory agents.

Oximes have been known for many years. They have been used chiefly as. derivatives to characterize aldehydes and ketones for the reason that most oximes are solid. Oximes have also found use in connection with synthetic methods, for example, to form amines on reduction, or nitriles on dehydration. However, extended searches through the scientific and patent literature have failed to unearth any disclosure or teaching that oximes possess desirable odorous and other qualities which might make them desirable olfactory agents for use in perfume compositions. Surprisingly, it has now been found that a limited number of oximes possesses such qualities.

The oximes which have been found useful in accordance with this invention are those of seven to l carbon atom 2 branched-chain ethylenic unsaturated hydrocarbyl aldehydes and ketones. Among specific oximes found to be suitable in accordance with the invention are one citral oxime; citronellal oxime; 2,6-dimethyl--heptenal oxime; 3-methylheptan-5-one oxime; octan-3-one oxime; 3,7-dimethyloctanal oxime; 2- methylheptan--one oxime; heptan-Z-one oxime; nonan-3-one oxime; octan-Z-one oxime and 2methyl-2-hepten-6-one ox- The specificity of the present finding can be seen from the fact that oximes having closely related chemical structure are not suitable for the purposes of this invention. Examples of such latter oximes are n-heptaldehyde oxime and n-nonanal oxime. Also, it is to be noted that oximes having less than six or more than carbon atoms are unsuitable for perfuming purposes.

The oximes useful in accordance with this invention possess a unique combination of olfactorily desirable properties. They are all either colorless (i.e., water-white) or only slightly colored, readily available, uniform in odor from batch to batch, nonirritating when used in accordance with this invention, stable and easy to use. These oximes possess truly unique odors not presently duplicated either by known natural or other synthetic odorants.

The oximes encompassed by this invention may be employed in a variety of perfume-containing compositions, such as fragrances or perfumes, perfume oils, toilet water, cosmetics, creams, detergents, soaps, lotions, space deodorants and other deodorants, etc.

The oximes of this invention are especially useful for imparting the quality of naturalness to perfume-containing compositions when used in formulations simulating natural oils such as lilac, lavender, etc.

The amounts of the hereinabove-identified oximes which may be used differ widely, mainly depending on the nature of the compositions and the desires of the perfume compounder. For purposes of illustration, it has been found that, in general, amounts from about 0.1 to about 80 percent by weight, based on the weight of the finished perfume-containing composition, give satisfactory results, amounts from about 0.1 to about l0 percent being especially satisfactory.

The oximes may be incorporated in perfume-containing compositions in conventional manners; hence, no special directions are deemed necessary to enable one skilled in the art to practice this invention. Nevertheless, in order to facilitate practice of this invention the following examples are given, by way of illustration and not by way of limitation. All parts and percentages are by weight, the percentages being based on the total composition, unless otherwise stated.

EXAMPLE I 3-Methylheptan-5-One Oxime This novel oxime was prepared as follows:

Into a 2-liter, 3-necked flask fitted with a mechanical stirrer, dropping funnel and condenser was charged 82.1 g. of hydroxylamine sulfate and 100 ml. of water. To this solution was added dropwise 1 18.5 g. of 33.7 percent sodium hydroxide at 5 30 C. When the addition was complete a solution of I28 g. of 3-methyl-5-heptanone in 300 ml. of ethyl alcohol was added dropwise at 30 C. The resulting mixture was refluxed for l hour at 80-85 C. The mixture was poured on a large volume of water. The organic material was separated and the water 10 phase extracted several times with toluene. The combined organic phases were washed once more with water. The solvent was removed under mm. of mercury pressure and the product distilled through a 37 mm. column packed with glass helices: b.p. 70 (0.7 mm.); 95.0 g.; m, 1.4519; Anal. Calcd.

5 for C H NO: %N, 9.92; Found 9.50. The infrared spectrum shows absorption at 3.35 (OH) and 6.10 (C= N) microns.

Carbonyl value 0.0.

The novel oxime has an intense green-leaf odor quite suggestive of crushed figue leaves. lt is useful as a base for the synthetic reconstruction of the odor of natural figue leaves absolute, as illustrated by the following formulation:

Coumarine 30 I-Icliotropine 20 Benzyl Valerianate 20 Estragole 60 J-methylheptan-S-one oxime 485 Linalool B0 Nonadienal 5 Raldeine gamma 300 Total 1,000

Raldeine is the registered trademark of Givaudan Corporation for methylionones.

The novel oxime of this example can be used as a total or partial substitute for natural figue leaves absolute. It has the following advantages over the natural products:

Lower cost Readily available Constant in odor (the natural product varies from crop to crop) Colorless (the natural product imparts an intense green color) Nonirritant (natural figue leaves absolute has been reporte as an irritant when in contact with the skin) Stable in soap, cosmetics, and aerosols.

The novel oxime itself is stable in soap, detergents, cosmetics, and aerosol. Under accelerated tests and a 6-month shelf test it does not give any signs of discoloration or change in odor. Its odor is unique in its likeness to figue leaves absolute and it cannot be replaced in the above formulation by any other known chemical or composition.

EXAMPLE ll Octan-B-One Oxime The oxime of this example is a known compound. lt possesses an intense green-earthy odor suggestive of crushed twigs and moss. It is useful as a base for the synthetic reconstitution of the odor of natural oak moss, as illustrated by the following formulation:

Coumarine H30 3-hydrnxy-Z-methyl-4H-pyran-4-one 27 Anisyl acetate 36 Cade oil l8 Cedarleaf American 90 Cedarwood American 540 Octan-J-one oxime 5.8M n-hexyl benzoate S40 lsopmpyl quinoline 45 Linalool 900 Linalyl isovalerate 990 Methyl acetophenone I80 Nonadienal 3 Raldeine gamma 360 Styrax soluble resin 250 Total [0,000

The oxime of this example can be used as a total or partial substitute for natural oak moss. It presents over the natural products the following advantages:

Lower cost Readily available and does not depend on natural products sometimes difficult to obtain Constant in odor (the natural product varies from crop to crop) Colorless (the natural product imparts a green-brown color) Stable in soap, cosmetics, aerosols (the natural product is unstable in aerosol).

The oxime of this example itself is stable in soap, detergents, cosmetics, and aerosol. Under accelerated tests and a 6-month shelf test it does not give any signs of discoloration or change in odor.

While there exist other synthetic reconstitutions of oak moss based on various chemicals, none possesses the intense green-earthy note of the oxime of this example; and it cannot be replaced in the above formula.

EXAMPLE Ill 2,6-Dimethyl--Heptenal Oxime This novel oxime was prepared as follows:

Into a 3-liter, 3-necked flask fitted with a mechanical stirrer, dropping funnel and condenser was charged 164.2 g. hydroxylamine sulfate and 200 ml. of water. To this solution was added dropwise 237 g. of 33.7 percent sodium hydroxide at 30 C. When the addition was complete a solution of 330 g. of 85 percent (by weight) 2,6-dimethyl-5-heptenal in 600 ml. of ethyl alcohol was added dropwise at 30 C. The resulting mixture was refluxed for 1 hour at 80-85 C. The mixture was poured on a large volume of water. The organic phase was separated and the water solution extracted with toluene. The combined organic phases were washed once more with water. The solvent was removed under 20 mm. of mercury pressure and the product distilled through a 37 cm. column packed with glass helices: b.p. 80l (0.9 mm.) m, l.4705; Sp. gr. 0.9028; Anal. Calcd. for C H NO: %N, 9.02; Found %N, 8.77, 8.59.

The infrared spectrum shows absorption at 3.30 (OH) and 6.05 (C =N) microns. Carbonyl value 0.0.

The novel oxime of this example has a floral odor suggestive of Gardenia flower.

it is useful as a base for the synthetic reconstitutions of the odor of the Gardenia flower, as illustrated by the following formulation:

Heliotropine lndol l Amyl cinnamic aldehyde Bcnzyl acetate Cinnamic alcohol 2.6-dim|:thyl-S-heptenal oxime 340 Laurinc 170 Linalool 7S Linalyl acetate 75 Phenyl ethyl alcohol 85 d-methylbenzyl acetate 60 Total l,000

Laurine is the registered trademark of Givaudan Corporation for hydroxycitronellal.

This composition has a floral odor suggestive of Gardenia flower. Since no absolute or essence can be extracted from Gardenia flowers any composition that simulates the odor of these flowers is highly desirable. 2,6-Dimethyl-5-heptenal oxime is extremely valuable and unique in its contribution to the natural character of the above composition and cannot be replaced by any other chemical.

The oxime of this example is stable in soap, detergents, cosmetics, and aerosols. Under accelerated tests and a 6- month shelf test it does not give any signs of discoloration or change in odor.

EXAMPLE lV Citral Oxime Versalide polycyclic musk Labdanum resin Citral oxime 645 Civette absolute l 3,7,l l-trimethyl-l,6,l0

-dodecatriene-3-ol Raldeine gamma I00 Total 1,000

Versalide is the registered trademark of Givaudan Corporation for l ,l,4,4-tetramethyl-6-ethyl-7-acetyl-l ,2,3,4- tetrahydronaphthalene.

The above oxime can be used in the same manner and in place of ambergris natural. It presents over the natural product the following advantages:

Lower cost Readily available Constant in odor (the natural product varies according to its origin) Facility of use (does not require being put into and aged in alcohol as does ambergris natural).

Citral oxime is stable in soap, cosmetics, and aerosols. Under accelerated tests and a 6-month shelf test it does not give any signs of discoloration or change in odor.

The odor of citral oxime is entirely new in the respect that up until now the odor of sea weed was very difficult to obtain from either chemicals or natural products.

EXAMPLE V Citronellal Oxime The oxime of this invention is a known compound.

The following formula exhibits the extremely important function of citronellal oxime in this type of composition based on the unusual qualities of odor character, which in turn indicates its unique application in perfumery:

Bergamot natural l5 Citral S Citronellal oxime 40 Lemon oil l0 Lemongrass redistilled 8 Limes distilled W.l. 5

Mandarinc messina 6 Orange bitter l0 Vanillin lignin 1 Total I00 The above formula utilizing 40 percent of citronellal oxime may be used as a replacement for verbena oil. The natural oil is not used to any great extent in perfumery today due to the poor yield of oil and the difflculty in the cultivation of the plant involving climatic conditions. The above formula or variations of it using citronellal oxime offers uniformity of odor, availability of material, and reasonable stability in price.

The leafy-green-rosy-citrus odor character of citronellal oxime makes it invaluable, both for citrus types of fragrances as well as straight florals and floral bouquets.

Citronellal oxime is stable in soap, cosmetics, and aerosols. The odor performance of this chemical in test samples shows excellent stability.

EXAMPLE V1 This novel oxime was prepared as follows:

Into a 1-liter, 3-necked flask fitted with a mechanical stirrer, dropping funnel and condenser was charged 82.1 g. of hydroxylamine sulfate and 150 ml. of water. To this solution was added dropwise 190 g. of 33.7 percent sodium hydroxide at 30 C. When the addition was complete a solution of 156 of 3,7-dimethyloctanal in 150 ml. of ethyl alcohol was added dropwise at 30 C. The resulting mixture was refluxed for 1 hour at 80-85 C. The mixture was poured on a large volume of water. The organic material was separated and the water layer extracted several times with toluene. The combined organic phases were washed once more with water. The solvent was removed under 20 mm. of mercury pressure and the product distilled through a 37 cm. column packed with glass helices: b.p. 9410l (0.7 to 0.9 mm.) 74.4 g.; m, 1.4512; Sp. gr. 0.8701; Anal. Calcd. for C l-l NO: %N, 8.18; Found: %N, 7.99.

The infrared spectrum shows absorption at 3.30 (OH) and 6.10 (C N) microns. Carbonyl value 0.0.

The following formula exhibits the uniqueness of the novel oxime of this example and how it may be employed in perfumery:

Undecanal in dipropylene glycol 2 Eugenol USP 10 Citronellol leavo l0 Geraniol 30 Geranium bourbon Geranium palmarosa 50 3,7-dimethyloctanal oxime 400 Phenyl ethyl alcohol 438 Raldeine gamma 10 Total 1,000

The novel oxime of this example contributes an earthygreen-rosy character which gives a naturalness of odor resembling that of freshly cut flowers. This unique combination of notes is virtually impossible to obtain by the use of existing perfumery materials.

The oxime of this example was found to be stable in soap, cosmetics, and aerosols. The basic odor character of this chemical held up well with no significant change on standing.

EXAMPLE V11 2-Methylheptan-6-One Oxime The oxime of this example is a known substance. The following formulation illustrates the importance of this oxime as an integral part of a synthetic jasmine:

Ncnanolide-l,4,l0% in dipropylene glycol 5 Amyl cinnamic aldehyde 200 Beeswax absolute 5 Benzyl acetate 250 Benzyl alcohol. pcrfumery grade 185 Benzyl propionate Celery seed oil 5 Eugcnol USP 5 lndolc 5 Z-mcthylheptan-b-one oxime 300 Methyl octinc carbonate, 10% in tlipropylcnc glycol 5 Para crcsol, 10% in dipropylcne glycol 10 Para cresyl phcnyl acetate 5 Total 1,000

The oxime of this example contributes an earthy-mustyfatty odor character which is an essential part of this composition. The oxime yields a naturalness which would be difficult to obtain with existing materials.

The oxime of this example was found to be stable in soap, cosmetic media, and aerosols,

EXAMPLE vm Heptan-2-One Oxime The oxime of this example is a known material.

The following base illustrates the synergistic effects contributed by the oxime of this example:

Anethol USP 5 p-anisaldehyde J0 Balsam copaiba gum 60 Civet absolute, 10% in dipropylene glycol 5 Ethyl nialonate 200 Folione, 10% in dipropylene glycol 15 Geraniol 0's 50 Labdanum soluble resin 150 Methyl acetophenone Heptan-Z-one oxime Phenyl acetaldehyde 50% in dipropylene glycol 10 Phenyl acetic acid 8 Total 1,000

EXAMPLE 1X Nonan-3-One Oxime The oxime of this example is a known material.

The oxime of this example has an odor suggestive of galbanum, lavender, and cucumber. It also has a characteristic odor which is natural, green, and fresh. In addition to galbanum, lavender, cucumber, other uses for this oxime are found in rose-geranium, jasmine, citrus, pine, and violet compositions. lts odor is very intense and persistent, as indicated by dry-down studies. Tests have also indicated that the oxime of this example has synergistic properties. The following application formula demonstrates the use of this oxime as a major perfume component and as a synergist:

alpha pinene 50 beta pinene Camphene S Myrcene 10 Carene delta 3 4S Dipentene S Isocyclo citral (2,4,6- trimethyl-S-cyclohexenl-carboxaldehyde and 2, 3,S-trlmetbyld-cyclohexen- 4-carboxaldehyde) Galbanum Oil Nonan-Il-One Oxime 500 Total L000 EXAMPLE x Octan-2-One Oxime.

The oxime of this example is a known material.

Octan-Z-one oxime has an odor suggestive of lavender, with a natural, earthy, green, weedy, fresh, clean background. In addition to lavenders and lavender fougere, this oxime is useful in amber-Orientals, rose-geraniums, jasmines, citrus and pine. its odor is intense and persistent. in addition, this oxime can act as a synergist. The following application formula will demonstrate the use of this oxime as a synergist and a major perfume ingredient:

Linalyl propionatc 5.0 Coumarin 2.0 Methyl coumarin 2.0 Versalide 45 Geraniol 2.0 Geranyl acetate 2.0 Geranyl propionatc 2.0 Linalool .5 Linalyl acetate 5.0 Menthanyl acetate 25.0 Methyl hexyl ketone 1.0 Tcrpinyl acetate 3.0 Lavandin pure 50.0 Octan-Z-onc oxime l00.0

Total 200.0

The oxime of this example was used in the above formulation for the following reasons:

I. lts odor has the power to give a fresh, natural, green character to the compound, in addition to enhancing the lavender notes.

2. it is stable in perfumes, cosmetics, etc., and its use in a formulation minimizes instability in the final product.

3. Its light color would minimize the undesirable color of the naturals.

4. Because it is a synthetic, its consistency and availability are insured, in addition to low cost.

EXAMPLE XI 2-Methyl-2-Hepten-6-One Oxime The oxime of this example is a known compound.

The oxime of this example has an odor suggestive of fresh citrus fruits, with a natural, bitter, herbaceous, leafy, green character. In addition to citrus type odors, this oxime can be used in lavenders, jasmines, muguets, rose, pine, and especially fig-type compounds. in addition to being very intense and persistent, this oxime has synergistic properties. The following formulation demonstrates its use as a major perfume component:

Undecyl Alcohol Octanal O.l Nonanal O.l Dccanal O.l Citral 6.5 Cilronellal 0.2 Citronellol l.0 Citronellyl Propionate l.5 Dipentene l0.0 Geranyl Acetate l.5 Lemon Terpenes 25.0 Linalool Cocur L5 Terpinyl Acetate 2.0 2-methyl-2hepten-6-one oxime 50.0

Total l00.0

The oxime of this example was used in the above formulation for the following reasons:

I. Due to its unique odor, this oxime blends well with the other natural materials in the formulation, bringing out their fresh, natural, green character.

2. Due to its proven stability in perfumes, soaps, and

cosmetics.

3. Due to its light color.

4. Because of its insured availability, consistency, and low cost.

EXAMPLE Xll Muguet Perfume A perfume oil having a muguet character was made by mixing together the following ingredients in the amounts given:

product 47 Z-methyl-Z-hepten-fiwne oxime 10 Total Laurine is a registered trademark of Givaudan Corporation for hydroxycitronellal.

The perfume oil of this example was incorporated to the extent of 1 percent in unperfumed soap stock. The soap used was a neutral white toilet soap. The fatty acids in this soap had the following composition:

Oleic and linolcic acids 45 Palmitic acid 30 Stearic acid l0 Lower fatty acids IS The perfume oil of this example was also incorporated, to the extent of 0.1 percent in unperfumed synthetic liquid detergents such as those marketed as Lux and Swan, and to the extent of 0.2 percent in unperfumed synthetic powder detergents such as that marketed as All.

. [n all cases, the finished soaps and synthetic compositions had materially enhanced green top note of muguet fragrance, as compared with the same formulations without the oxime.

EXAMPLE Xlll Soaps and Synthetic Detergents A soap cologne was made by mixing together the following ingredients in the amounts given:

Petitgrain oil 225 Spike lavender oil 50 Bergamot oil I50 Lemon oil I50 Lemongrass oil 75 Methylnaphthyl ketone 40 Rosemary oil 60 Geranium oil I00 Citral I00 Citral oxime 50 Total 1,000

The soap cologne had a bright and more appealing odor, with an enhanced citrus character, as compared with the same perfume without the citral oxime.

The soap cologne of this example was incorporated to the extent of l percent in the unperfumed soap stock used in example XII. The soap cologne of this example was also incorporated to the extent of 0.] percent, in synthetic liquid detergents and 0.2 percent in synthetic powder detergents.

In all cases, the finished soaps and synthetic detergent com- In all cases, the finished soaps and synthetic compositions positions had a citrus odor which was much brighter and more had a pleasing leafy effect, as compared with the same appealing than the same compositions without the citral oxproducts not containing the oxime of this example.

lme.

EXAMPLE XVII EXAMPLE XIV Muguet Soap Perfume Perfume A perfume composition was prepared by mixing the follow- A perfume composition was prepared by mixing the following ingredients in the stated amounts: ing ingredients in the stated amounts: l0

Terpineol 47 Benzyl isoeugenol 20 gg'gztgl ggiri Coumarin l0 Musk amhrette 30 Citmncllol A l Bergamm a 75 :herllyllacetaldehyde dlmethyl 24 Linalyl acetate 125 W a Garanium 0 Algeria I lexylclnnamlc aldehyde 22 Spike lavender oil 20 i b R 2; Lemon oil 200 us am N 8 Lime oil 130 lndolene, Roure-Dupont, New" on 60 (a condensation product orange him" 00 between lndole and hydroxy Orange oil, sweet I00 g"?" 23 Rosemary oil 20 enzom 24 Clary sage oil 20 ('ananga Cmal Mime l0 2'methyl-2-heptcn-6-one oxlme I 50 Total 000 1 25 The finished perfume oil was suggestive of a freshly crushed The gi l perfume was of the muguet type a cool' lemon peel and had an improved and more lasting quality and green 8 appeal than the same perfume without the citral oxime. EXAMPLE Xvm EXAMPLE Xv A perfume composition was prepared by mixing the follow- A perfume composition was prepared by mixing the followmg mgred'ems m the Stated amounts: ing ingredients in the stated amounts:

Benzyl acetate 250 Hexylcinnamic aldehyde 1? Coumarln 20 Cananga oil l7 Musk amhrctte 25 Linalool 1 7 Vanillin l0 Laurine I67 Tolu balsam soluble resin 50 Ph n l h l al ohol 167 Benzoin soluble resin 50 Methyl salicylate 23 Bergamot oil In Methyl naphthyl ketone l7 Brazilian Bois de Rose oil 50 40 Gamma nonalactonc 25 Lavandin oil 50 Decanal (l0% in diethyl Lavender oil 500 Phthalate) l7 Petitgrain oil SA. 20 Ylang oil 67 Rosemary oil 50 Musk xylol 8 Thyme oil. red 25 Eugenol B Menthanyl acetate 50 2,6-dimethyl-5-heptenal oxime S0 Trimethyl hexyl acetate 80 m 000 Octan-3-one oxime 10 Total 1,000

The resulting perfume was of the gardenia type, suitable for use in soap and having a fresher, floral character than the w od h The addition of the ammo lends a green 0 y note to t e Same perfume without the oxime.

lavender composition while not altering the overall fragrance.

EXAMPLE XV] EXAMPLE XIX A perfume composition was prepared by mixing the followe a e mixin the follow- A perfume composmon was pr p r d by g mg ingredients in the stated amounts:

ing ingredients in the stated amounts:

Benzyl acetate A my irlnmimlc aldehyde m Hexylcinnamic aldehyde 68 dl rnethyl acetal I50 Cananga oil 22 Cltronellol 0 Linalocl 223 Ethyl pelargonatc I50 Gamma-undecalactonc 2 Geranlol 6O Laurine Geranyl formate 20 Musk ambt'ette 22 Geranyl acetate 2:3 Hydroxycitronellal-methyl- Geranium Bourbon 0 Anthranilate Schiff base 2 Lu a yl u m Phenylethyl alcohol 212 Mimosa Absolute p-Cresylphenyl acetate 10% 2 Phenyl Acetic Acid Sandela 45 Phenyl Ethyl Acetate Ylang oil 20 Phenyl Ethyl Alcohol '00 Z-methylheptan-fi-cne oxime 50 Rhodinol 200 Total 000 Rhodinyl Acetate S0 Heptan-B-One Oxime l0 Total 1,000 Sandela ls the reglstered trademark of Glvaudan Corpora- 70 tion for isocamphylcyclohexanols polycyclic alcohol. The oxime blends well with this rose composition imparting The perfume had a jasmine character and when incora natural character to the fragrance. porated in soap and detergents as set forth in example XII, was The rose composition of this example was incorporated in found to be quite suitable. The asmine note was enhanced the unperfumed soap stock,. the liquid and powder detergents substantially by the oxime, which also imparted an unusually as described in example XI]. fine, green, floral character to the perfume.

EXAMPLE XX Talcum Powder A citrus base formulation was made by mixing together the following ingredients in the amounts indicated:

Benzyl isoeugenol 20 Coumarin crystals 10 Musk ambrette 30 Bergamot oil 200 Geranium oil l Lavender spike oil 20 Lemon oil 200 Lime oil I30 Ncroli oil 160 Orange oil bitter 100 Orange oil sweet 60 Rosemary oil 20 sage claty oil 20 Citronellal oxime 20 Total l,000

The above perfume mixture and the same formulation without the oxime was incorporated into a talcum powder base in concentrations of 0.5 percent by weight. Upon comparison of these cosmetic products it was found that the addition of citronellal oxime improved the odor, enhancing the citrus character of the fragrance and giving a lasting and pleasing effect when applied to the skin.

Citronellal oxime may be used in perfume compositions in concentrations of from 0.l to 85 percent by weight depending upon the effect desired or the purpose intended. High concentrations of oxime would be used, for example, in aerosol formulations. The recommended use normally for this oxime is in the range of 0.1 to percent by weight.

EXAMPLE XXI Hand Lotion A floral perfume of the jasmine type was made by mixing together the following ingredients in the amounts indicated:

Benzyl acetate Hexylcinnamic aldehyde Cananga oil 22 Linalool 223 Gamma-undccalactone 2 Laurine l l2 Musk ambrctte 22 Aurantiol 2 Phenylethyl alcohol 2 l 2 p-cresylphenyl acetate l0% 2 Sandela 45 Ylang oil Nonan-3-one oxime 50 Total L000 Aurantiol is a registered trademark of Givaudan Corporation for hydroxycitronellal-methylanthranilate Schiff base.

This perfume mixture was incorporated into a standard hand lotion base to the extent of 0.5 percent by weight. Upon comparing this cosmetic preparation with one in which the jasmine perfume did not contain nonan-3-one oxime, it was found that the oxime enhanced the green top note of the fragrance and gave an overall improvement to the odor especially when the lotion was applied to the skin.

Ethyl hexyl ketone oxime may be used in perfume compositions in concentrations of from 0.1 to 85 percent by weight depending upon the effect desired or the purpose intended (see aerosol formulation). The recommended use is normally in the range of 0.l to 10 percent by weight.

EXAMPLE XXII Bath Oil Terpineol Laurine 50 Total L000 The above perfume mixture and the same formulation without the oxime was incorporated into an unperfumed bath oil to the extent of IO percent by weight. This cosmetic preparation was evaluated from water warmed to 50 C. in order to simulate bath conditions. It was found upon comparison of the bath oil preparations that the addition of heptan-2-one oxime enhanced the cool green top note of the muguet and tended to add to the diffusibility of the fragrance emitted from the wanned water.

Z-Heptanone oxime may be used in perfume compositions in concentrations of from 0.1 to percent by weight depending upon the effect desired or the purpose intended. The recommended use is normally in the range of 0. l to 10 percent by weight.

EXAMPLE XXIII Hand Lotion A rose perfume was made by mixing together the following ingredients in the stated amounts:

lrisone is a registered trademark of Givaudan Corporation for ionones.

This perfume mixture was incorporated into a standard hand lotion base to the extent of 0.5 percent. This cosmetic preparation was compared with one in which the rose perfume did not contain 3,7-dimethyloctanal oxime. It was found upon evaluation of the lotion that the presence of the oxime improved the rose fragrance, lending a fresh green note to the perfume.

3,7-Dimethyloctanal oxime may be used in fragrance compositions in concentrations of from 0.1 to 85 percent depending upon the effect desired or the purpose intended. The recommended use normally is in the range of 0.l to 10 percent.

EXAMPLE XXIV Aerosol Fragrance A fragrance for use in an aerosol air freshener was made by mixing together the following ingredients in the stated amounts:

J-methylheptan-S-one oxime 850 lsobornyl acetate 60 lrisone S Patchouli oil I] Lavandin oil 50 l-carvone 8 Cassie absolute 5 3-hydroxy-2-methyl-4H pyran-4-onc 2 Versalide 7 Total L000 The above fragrance has a sweet pine-lavender odor wherein the 3-methylheptan-5-one oxime blends very well.

EXAMPLE XXV Jasmine Soap Fragrance The following jasmine soap perfume was compounded to demonstrate the use of 3-methylheptan-5-one oxime in soap:

Benzyl acetate 230 Hexylcinnamic aldehyde 68 Cananga oil 32 Linalool 233 gamma undecalactone 2 Laurine l 12 Musk ambrette 22 Hydroxycitronellal methyl Anthranilate Schiff base 2 Phenylethyl alcohol 2l2 p-cresyl phenylacetate 2 Sandalwood oil 45 Y lang oil 3-methylheptan-5-one oxime 20 Total 1,000

The resulting jasmine soap fragrance was incorporated to the extent of 1 percent in the unperfumed soap stock referred to in example XII.

The resulting jasmine soap had a persistent and pleasing green note which was not present in the soap with the perfume composition without 3-methylheptan-5-one oxime.

As already noted, many oximes are well-known chemicals and processes for their preparation are known. In general, therefore, the oximes employed in accordance with this invention are made by treating the corresponding aldehyde or ketone with an equivalent amount of hydroxylamine. The latter may be formed, in situ, by liberation from a hydroxylamine salt, such as hydroxylamine sulfate or hydroxylamine hydrochloride, by treatment with a base. The resulting oximes are purified by distillation.

Details of the preparation of certain novel oximes possessing unobvious properties are given in examples I, Ill and VI.

While I have described my invention in detail in its presently preferred embodiments, it will be obvious to those skilled in the art that various changes and modifications may be made therein, particularly in the actual formulations employed, without departing from the spirit or scope of my invention. I aim in the appended claims to cover all such changes and modifications.

Iclaim:

l. A perfume-containing composition comprising an'olfactorily effective amount of an oxime of a branched-chain ethylenic unsaturated hydrocarbyl aldehyde or ketone having from seven to 10 carbon atoms.

2. The perfume-containing composition of claim R, wherein said oxime is selected from the group consisting of citral oxime; citronellal oxime; 2,6-dimethyl-5-heptenal oxime; 3- methylheptan-S-one oxime; octan-3-one oxime; 3,7-dimethyloctanal oxime; 2-methylheptan6-one oxime; heptan-Z-one oxime; nonan-3-one oxime; octan-2-one oxime and Z-methyl- 2-hepten-6-one oxime.

3. The perfume-containing composition of claim 1, wherein said oxime is citral oxime.

4. The perfume-containing composition of claim 1, wherein said oxime is 2-methylheptan-6-one oxime.

5. The perfume-containing composition of claim I, wherein said oxime is 2-methyl-2-hepten-6-one oxime.

6. The perfume-containing composition of claim I, wherein said oxime is octan-Z-one oxime.

7. The perfume-containing composition of claim 1, wherein said oxime is 3-methylheptan-5-one oxime.

8. A perfume blend containing an olfactorily effective amount of an oxime of a branched-chain ethylenic unsaturated hydrocarbyl aldehyde or ketone having from seven to 10 carbon atoms.

9. The perfume blend of claim 1 wherein said oxime is citral oxime.

10. The perfume blend of claim 1 wherein said oxime is 2- methylheptan-6-one oxime.

11. The perfume blend of claim 1 wherein said oxime is 2- methyl-2-hepten-6-one oxime.

12. The perfume blend of claim 1 wherein said oxime is octan-2-one oxime.

13. The perfume blend of claim 1 wherein said oxime is 3' methylheptan-S-one oxime. 

2. The perfume-containing composition of claim 1, wherein said oxime is selected from the group consisting of citral oxime; citronellal oxime; 2,6-dimethyl-5-heptenal oxime; 3-methylheptan-5-one oxime; octan-3-one oxime; 3,7-dimethyl-octanal oxime; 2-methylheptan-6-one oxime; heptan-2-one oxime; nonan-3-one oxime; octan-2-one oxime and 2-methyl-2-hepten-6-one oxime.
 3. The perfume-containing composition of claim 1, wherein said oxime is citral oxime.
 4. The perfume-containing composition of claim 1, wherein said oxime is 2-methylheptan-6-one oxime.
 5. The perfume-containing composition of claim 1, wherein said oxime is 2-methyl-2-hepten-6-one oxime.
 6. The perfume-containing composition of claim 1, wherein said oxime is octan-2-one oxime.
 7. The perfume-containing composition of claim 1, wherein said oxime is 3-methylheptan-5-one oxime.
 8. A perfume blend containing an olfactorily effective amount of an oxime of a branched-chain ethylenic unsaturated hydrocarbyl aldehyde or ketone having from seven to 10 carbon atoms.
 9. The perfume blend of claim 1 wherein said oxime is citral oxime.
 10. The perfume blend of claim 1 wherein said oxime is 2-methylheptan-6-one oxime.
 11. The perfume blend of claim 1 wherein said oxime is 2-methyl-2-hepten-6-one oxime.
 12. The perfume blend of claim 1 wherein said oxime is octan-2-one oxime.
 13. The perfume blend of claim 1 wherein said oxime is 3-methylheptan-5-one oxime. 